Dye salts of anionic metal complex dyes of the benzeneazoacetoacetyl alkyl amide series and organic amine nitrogen bases



United States Patent 600/65 23 Claims. (Cl. 260-145) ABSTRACT OF THEDISCLOSURE Anionic metal complex dye/nitrogen base salts, the dye ofwhich is a benzene-azo-acetoacetyl-alkyl amide dye, have good solubilityin organic solvents. Polymers colored with the dye salts have excellentfastness properties.

This invention relates to dye salts from an anionic metal complex dye ofthe benezene-azo-acetoacetyl-alkyl amide series and a nitrogen base anda process for their production.

The anionic metal complex dye is based upon a metalfree dye of theformula where:

R represents a carboxylic or sulphonic acid group,

R represents a substituent capable of metal complex formation, and

R represents a substituted or unsubstituted alkyl radical, preferably analkyl radical having at least 5 or, more particularly, 6 to 14 carbonatoms. The nucleus A may bear further, non-dissociating substituents.

This dye (I) may be employed as a 1:1 complex, for example withchromium, copper or nickel as metal atom, or as a 1:2 complex, forexample with chromium or c0- balt as metal atom.

The process for the production of the new dye salts comprises reactingone mole of an anionic metal complex dye of thebenzene-azo-acetoacetyl-alkylamide series with 1 mole of a nitrogenbase. Especially suitable dye salts are obtained when a 1:2metal-complex dye of 1 mole of a dye of Formula I and 1 mole of anothermetallizable azo dye and 1 atom of chromium or cobalt, or, when a 1:2metal complex dye of 2 moles of a dye of Formula I and 1 atom ofchromium or cobalt is reacted with a nitrogen base.

The following asymmetric 1:2 metal complex dyes are especially suitable,for example those of the formula where X represents O- or -COO-, Yrepresents O--, COO, -NH 0 r where:

R stands for a substituted or unsubstituted alkyl or aryl radical, suchas a phenyl or naphthyl radical,

R stands for the radical of a diazo compound having a metallizable groupin ortho position to the azo group,

R stands for the radical of a coupling component having a. metallizablegroup in adjacent position to the azo group, and

Me stands for a metal atom, for example a chromium or cobalt atom,

the ring A may bear further substituents, for example chlorine, bromine,fluorine, nitro, cyano, trifluoromethyl, alkyl radicals having 1 to 5carbon atoms, alkoxy radicals having 1 to 5 carbon atoms, low molecularalkylsulphonyl, phenyl or low molecular alkanoylamino. In Formula IIIeach alkyl (other than for R and the alkyl of each alkoxy substituentmay be lower alkyl.

Illustrative dyes (III) are the asymmetrical 1:2 cobalt complex dyes offormula where The 1:1 complexes have the formula OMeO-CCH;

R1 N=NC A ('JO-N H while the symmetric 1:2 metal complex dyes used forthe production of the dye salts are of the formula 4 where Me representsa metal atom, preferably a chromium colorations obtained in thesematerials have excellent or cobalt atom. fastness to light, water,washing, perspiration, hydrosul- Examples of other metallizable azo dyesare those of phite, sublimation and fats.

the benzene-azo-benzene, benzene-azo-naphthalene, ben- In Example 5 ofFrench Patent 1,227,024 the produczene azo-pyrazolone,benzene-azo-aminopyrazole, ben- 5 tion of a dye salt is describedwherein a 1:2 cobalt comzene-azo-acetoacetylamide andnaphthalene-azo-naphthalplex dye having in the metal-free form theformula ene series, all of which bear groups capable: of metal complexformation, in particular carboxyl, amino and hy- H droxyl groups inortho, ortho position to the azo group. I O CH SOPCH, Dyes of thisdescription are described, for example, in the H000 N=N followingpatents: O

United States Patent 3,040,019, filed on Dec. 11, 1959; Swiss Patents303,283, filed on Mar. 26, 1952; 316,751, (a) filed on May 22, 1953;316,752, filed on. July 3, 1953; filed On y 1953; 339,634, filed 011 isreacted with Rosinamine D (dihydroabiethylamine). 353,103, filed 011Mali 1957; ed On The resulting dye salt is suitable, among other uses,for 1957; German Patents 535,472, filed n ly the coloration of surfacecoatings and the spin dyeing of 1927; 704,541, filed on Oct. 27, 1935;709,631, filed on cellulose acetate, 1937; filed 011 Allg- 1938;715,948, For the purposes named above it is important that dyes filedOX1 1938; 723,292, filed 011 r- 19, 1937; 20 or dye salts should be usedwhich are well soluble in filed On 1938; d 0n organic polar solvents anddo not tend to crystallize in 2, 1942; fi n M y 1942; 0, filed thesesolvents. In mechanical production methods good on May 9, 1954;1,011,396, filed on Dec. 29, 1955; solubility is of great advantagebecause dye salts of low 1,044,023, filed on Dec. 14, 1955. solubilityoften lead to interference in operation.

The nitrogen bases used as starting materials are organic It wassurprising to find that dye salts based upon an amines which may becolorless or colored. For example, anionic metal complex dyecorresponding in the metalprimary or secondary aliphatic amines havingat least 4 free form to Formula I and a nitrogen base should exhibit orpreferably 10 to 18 carbon atoms can be used, or better solubility inorganic polar solvents than the dye salt alternatively basic dyescontaining, for example, hydrazincontaining the metal complex dye which,in the metal-free ium, ammonium, cycloimmonium or aminoxide groups,form, corresponds to Formula a. such as the dyes of the acridine,auramine, rhodamine, Especially good dye salts are, for example, thosecormalachite green and triphenylmethane series. responding to theformula Ra Ra CODE 9 RPC Q\ /O@Ra e N- oo --N o 0 OH 11 ll Compoundscontaining a hydrazinium group are dis- In the following examples theparts and percentages closed, for example, in French Patent 1,325,176,filed on are by weight and the temperatures in degrees centigrade. Apr.20, 1962; in French patent of addition 81,967 to French Patent1,325,176, filed on Apr. 21, 1962; and in EXAMPLE 1 Belgian Patents 695, fi On p 1963; 633,447: 18 parts of the dye obtainable according tothe particufiled on June 1 1963; 638,438, filed 011 1963; lars ofExample 1 of French Patent 1,331,221, filed On filed 011 1963; and645,280 filed on Aug. 20, 1962, which contains cobalt in a complex bond,Mar. 16, 19 are dissolved with 2 parts of sodium hydroxide in 500 Dyeswhose basic character is due to the presence of Parts f Water at 5 ASolution f parts f an external o i m or cycloimmonium group, ord-amineBExtra (Colour Index No. 45170 and 10 parts of which are derivedfrom the Fischer base, are described, 55 30% hydrochloric acid in 3Parts f water i run t p in German Patents 1,011,396 filed on the firstsolution. A red precipitate forms immediately. 1955, and 1,044,026,filed on 1955; and 111 After the acid reacting suspension has cooled,thisisfiltered German Auslegeschrift 1,045,969, filed on Feb. 8, 1956.ff t pH 1 2, washed with water, dried and ground, upon y containingamifloxide groups are described, for Which it is obtained as a redpowder which is highly solup in Belgian Patfillt filed on 1960- 50 bleon polar organic solvents, such as alcohol, ketones,

Heterocyclic Compounds of aromatic character containacetic acid alkylesters and ethers, ethyl alcohol, butyl ing nitrogen can also be used,eXamPle 01182016, 3113' alcohol acetone, cyclo'hexanone, ethyl acetate,amyl ace- 101e,pyrrolepyrazole,imidazolenhiodiazomoxadiazole, tate,methyl glycol, ethyl glycol, diacetone alcohol and 1,2,3- and1,2,4-triazole, tetrazole pyridine piperidine, i h py P P mofpholine, pyPY 65 This product is suitable for the coloration of plastics in pypyrimidine and py compounds; if and surface coatings, for examplenitrocellulose and vinyl preferred these can be used in the form ofcondensed polylacquers, in which it gives fiery red shades of goodfastness cycles, for example a benzoxazole, benzthiazole, indole, tolight, fats and top finishes. It can also, be used for the indazole,benzimidazole, quinoline or isoquinoline cyclic coloration offiber-forming materials in solution in organic system. solvents, forexample cellulose acetate, polyesters or poly- These dye salts, byvirtue of their good solubility in oracrylonitrile, which aresubsequently spun into filament. ganic solvents, are suitable for thecoloration of high The following table gives details of the structure offurmolecular materials, for example natural and synthetic ther dyesalts. Column (I) gives the structural composiresins, plastics, rubber,and solutions of these materials pretion of the acid metal complex dye,column (II) the type pared for spinning or for use as surface coatings.The of base used and column (III) the shade of the colorations obtainedwith the dye salts in vinyl lacquer. The Index, second edition, 1956,under which the dye or base figures in column (II) refer to the numbersin the Colour is described.

TABLE Ex. No. (1) (II) (III) 2 1:1 coppelr complex of Example 4 ofFrench Patent Rhodamine B 0.1. 45170 Red.

3 1:2cob a1t complex otExample 1 of French Patent Rhodamlne 40.1) 0.1.45160 Red.

4 1:2 chiomium complex of Example 2 of French Rhodamlne B 0.1. 45170Red.

Patent 1,331,221.

5 1:1 copper complex of Example 3 of French Patent do Red.

6 1:2'coba1t complex oi 2-amino-1 hydroxy-4-nltro- Dodecylamlne Yellow.

benzeneo-carboxylic acid- 1-acetoacetylaminooctane.

7 1:1 copper complex of 2-amino-1-hydroxy-4-nitro- Stearylamlne Do.

' benzene-o-carboxylic acid- 1-acetoacetylaminooctane.

8 1:2 chromium complex of 2-amino-1-hydroxy-4- Dleyclohexylamine Do,

nitrobenzeneG-carboxylic acid- 1-acetoacetylamino-octane.

9 1:2 cobalt complex of 2-amlno-1hydroxy-4-nitro- Di-o-tolyl-guanidlneDo.

benzene-fi-sulphonic acid-1-acetoacetylamino- 1 dodecane. V v

10, 1:2 chromium complex of 2-amino-1-hydroxy-4-Benzyl-isothiuronlumchloride D0.

nitrobenzene-o-sulphonic acid 1-acetoacetylv amino-dodecane.

11 1:2 ggllaiglcomplex of Example 11 of French Patent Auramine G 0.1.41005 Do.

12 1:2cob'alt complex of Example 11 of French Patent Malachite Green0.1. 42000 Green.

13 1:2 copper complex of Example 11 of French Acridine Yellow G 0.1.46025 Yellow.

Patent 1,331,221.

14 1:2 cobalt complex of Example 26 of French Rhodamine B 0.1. 45170Violet.

. Patent 1,331,221. 15 1:2 cobalt complex of equimolar amounts of the doR d,

acid dyes 2-amino-l-hydroxy'4-nitrobenzene-6- carboxylicacid-d-acetoacetyl-amino-Z-ethylhexane and2-amino-l-hydroxy-4chlorobenzene 1-phenyl-3-methyl-5-pyrazolone. 16 1:2cobalt complex of equlmolar amounts of the .do Red,

' acid dyes 2-amino-1-hydroxy-4-nltrobenzene-ficarboxylic acid-1-acetoacetylamino-2-ethylhexane and2-amino-1-hydroxy-4,6-dichlorobenzene l-phenyl-S-methyl-fi-pyrazolone. 11;2 cobalt complex of equimolar amounts of the -do Red.

' .acld dyes 2-amlno-1-hydroxy-4-nitrobenzene-ficarboxylic acidl-acetoacetylamino-2-ethylhexane and -2-amlno-1-hydroxy-3,4,6-trichl0rwv benzene- 1-phenyl-3-methyl-5-pyrazolone. 18 1:2 cobalt complex ofequlmolar amounts of the .....do

acid dyes 2-amino-1-hydroxy-4-nitrobenzene-G- carboxylicacid-d-acetoacetylamino-2-ethylhexane and 2-amino-1-hydroxy-4-nitrmbenzene-d-phenyl-3-methyl-fi-pyrazolone. 19 1:2 cobalt complex ofequlmolar amounts of the dc Blue-red.

acid dyes 2-amino-1-hydroxy-4-nitrobenzene-6- carboxylicacidl-acetoacetylarnino-2ethylhexane and2-amino-1-hydroxy-5-nitro-benzene-d-phenyl-3-methyl-5-pyrazolone. 20 1:2cobalt complex of equimolar amounts of the do R d,

acid dyes Z-amino-l-hydroxy-4-nitrobenzene-6- carboxylicacid-l-acetoacctylamino-2-ethylhexane and2-amin0-1-hydroxy-4-nitro-6-chlorobenzene-*l-phenyl-3-methyl-5-pyrazolone.21 1:2 cobalt complex of equimolar amounts 0! the do R d,

acid dyes 2-amino-l-hydroxy-4-nitr0benzene-6- carboxylic acid1-aceto-acetylamino-Z-ethylhexane and 2-amino-1-hydroxy-4-nitrobenzene1-acetoacetylamino-benzene.

Red.

2 a do 02N -N=N-N Orange.

23 1:2 chromium complex of equimolar amounts of thefl-metlioxy-l-aminoprop'mp 0 u acid dyes2-amino-l-hydroxybenzene-G-carboxylic acid 1-acetoacetylaminopcntane and2- amino-l-hydroxy-4-bromobenzene l-(1- naphthyl)-3-methyl-5-pyrazolone.

24 1:2 chromium complex ofequimolar amounts of the The dye of Example 1of German Patent l,0ll,396 O acid dyes2-amino-l-hydroxy--chlorobenzenefi-sulphonic acid-1-acetoacetyl-amino-dodecane and 2-arnino-l-hydroxy-4,6-dibromobenzene3-methyl-5-pyrazolone.

25 1:2 cobalt complex of equimolar amounts of the Zapon Fast Blue 3G0.1. 51005 Olive.

acid dyes 2-amino-1-hydroxy-4-bromobenzenetw-carboxylic acid1-acetoacetylaminotetradecane and 2-amino-l-methoxy-4,6-dinitrobenzene-1-(2-tetrahydronaphthyl)-3-methyl-5- pyrazolone. v

26 1:2 cobalt complex of equimolar amounts of the Astrazon Red GB 0.1.48020 Red,

acid dyes 2-amino-1-hydroxy-4methylbenzene- G-carboxylic acid1-acetoacetoacetyl-aminodecane and 2-amino-1-hydroxy-4-methoxybenzene1-iso-propyl-3-methyl-5-pyrazolone.

27 1:2 cobalt complex of equimolar amounts of the Thioflavine 0.1. 49005Yellow.

acid dyes 2-amino-1-hydroxy-4-tert. butylbenzene-frcarboxylicacidl-acetoacetyl-aminohexane and 2-amino-1-hydroxy-4-nitro'6-methylbenzene-d-(2,5-dich1oro)-phenyl-3- methyl-fi-pyrazolono.

TABLE-Continued Ex. No. (I)

28 1:2 cobalt complex of equimolar amounts of the acid dyes2-amino-1-hydroxy-4-chlorobenzene-6- carboxylic acid-1-acetoacetyl-amino-octane and2-amino-l-hydroxy-benzene-4methylsulp1hone 1-(3-cyan0phenyl)-3-methyl-5-pyrazone.

:2 chromium complex of Example 22 of French Patent 1,331,221.

:2 chromium complex of Example 24 of French Patent 1,331,221.

:2 cobalt complex of Example 26 of French Patent 1,331,221.

:2 ggllneglzfilcomplex of Example 27 of French Patent :2 cobalt complexof Example 28 of French Patent :2 cobalt complex of Example 29 of FrenchPatent 1,331,221.

:2 chromium complex of equu'nolar amounts of the acid dyesZ-amino-1-hydroxy-benzene-6- carboxylic acidl-acetoacetylaminoundecaneand Z-amino-1-hydroxy-4-nitro-benzene- 4- tert.butyl-1-hydrow-benzene.

:2 cobalt complex of equimolar amounts of the acid dyes2-amino1-hydroxy--nitrobenzone-6- carboxylic acid-1-acetoaeetylamino-hexane and 2amino-1-hydroxy-i-chlorobenzene1,3-diaminobenzene.

Benzylmorpholinc (II) (III) Chrysoidine GS C.I. 11270 Orange.

1-amino-2-hydroxy-propaue Light brown.

Application Example A.A solution is prepared of parts of vinylchloride/vinyl acetate copolymer, for example Vinylite VMCH (registeredtrademark of Union Carbide Ltd.), 70 parts of methyl ethyl ketone and 10parts of ethylene glycol. To this is added a solution of 0.5 part of thedye obtained in accordance with Example 1 in 10 parts of the identicallacquer solution. The pigmented lacquer is diluted with parts of a 1:1solution of methyl ethyl ketone and cyclohexane, cast on aluminiumsheeting and air dried. The coating has a bright fiery red shade andshows good adhesibility with good fastness to wet rubbing, fats and topfinishes and excellent fastness to light.

Application Example B.--100 parts of cellulose acetate containing 54-55%of cleavable acetic acid are mixed with 300 parts of solvent, forexample a mixture of 275 parts of acetone and 25 .parts of methanol; andafter being well stirred, the solution is left overnight to swell. Nextday 1 part of the dye obtained according to Example 1 is dissolved inparts of the same solvent and this solution is added to the celluloseacetate solution with continued stirring until 60 parts of the solventhave evaporated. The solution is filtered through cotton and a cottonwool filter press and spun in the same way as undyed cellulose acetate.The resulting filament is dyed in a fiery red shade.

Formulae of the representative dyes of the foregoing examples are asfollows:

Example 1:

Having thus disclosed the invention what I claim is:

1. An anionic metal complex dye organic amine nitrogen base salt, thedye of which is a benzene-azo-acetoacetyl-alkyl amide dye wherein thealkyl has from to 14 carbon atoms.

2. A dye salt according to claim 1 wherein the nitro gen base iscolorless.

3. A dye salt according to claim 1 wherein the nitrogen base is colored.

4. A dye salt according to claim 1 consisting of a member selected fromthe group consisting of (a) a 1:1 chromium, 1:1 copper and 1:1 nickeland a 1:2 chromium and 1:2 cobalt complex dye which is based upon ametal free dye of the formula wherein:

R is a member selected from the group consisting of a carboxylic and asulfonic acid group; R is a member selected from the group consisting ofan alkyl radical having 5 to 14 carbon atoms; nucleus A is otherwiseeither unsubstituted or substituted, any substituent being selected fromthe group consisting of chloro, bromo, fiuoro, nitro, cyano,trifluoromethyl, alkyl radicals having 1 to 5 carbon atoms, alkoxyradicals having 1 to 5 carbon atoms, lower alkylsulfonyl, phenyl andlower alkanoylamino; and (b) a nitrogen base selected from the groupconsisting of a primary and secondary aliphatic amine having 4 to 18carbon atoms; basic dye containing a hydrazinium, ammonium orcycloimmonium group; dye of the acridine, auramine, rhodamine, malachitegreen or triphenylrnethane series and a heterocyclic compound ofaromatic character.

5. A dye salt according to claim 4 wherein (a) consists of a memberselected from the group consisting of a 1:2 chromium and 1:2 cobaltcomplex dye of the formula wherein:

X is a member selected from the group consisting of -O- and COO--;

Y is a member selected from the group consisting of -O, COO, NH- and Ris a phenyl radical;

R is the radical of a diazo compound of the benzene series, having X inortho-position to the azo group;

R is the radical of a coupling component having Y in ortho-position tothe azo group and being selected from the groups consisting of thebenzene, naphthalene, pyrazolone, aminopyrazol and acetoacetylamideseries; and

Me is' a member selected from the group consisting of chromium andcobalt.

6. A dye salt according to claim 1 wherein the anionic metal complex isa member selected from the group consisting of a 1:1 chromium complex, a1:1 copper complex a 1:1 nickel complex, a 1:2 chromium complex and a1:2 cobalt complex, based upon a dye, in metal-free form, which is aZ-amino-1-R -benzene-6-R l-acetoacetylamino-alkane, wherein R is amember selected from the group consisting of a carboxylic and a sulfonicacid group, R is a substituent capable of metal complex formation, thealkane has from 5 to 14 carbon atoms and the henzene nucleus is freefrom further dissociating substituents.

7. A dye salt according to claim 1 wherein the dye is a 1:2 metalcomplex of (a) one mol of a 2-amino-1-R benzene-6-Rl-acetoacetylaminoalkane, wherein R is a member selected from the groupconsisting of a carboxylic and a sulfonic acid group, R is a substituentcapable of metal complex formation, the alkane has from 5 to 14 carbonatoms and the benzene nucleus is free from further dissociatingsubstituents; (b) one mol of another metallizable azo dye; and (c) oneatom of a metal se lected from the group consisting of chromium andcobalt.

8. A dye salt according to claim 7 wherein at most one metal complexforming substituent is an amino substituent and that substituent is inthe other metallizable azo dye.

9. A dye salt according to claim 6 wherein the dye is a 1:2 metalcomplex of 1 atom of metal selected from the group consisting ofchromium and cobalt and two mols of the same dye.

'10. A dye salt according to claim 9 wherein each metal linkage formedby a metal complex forming substituent is an O- bridge.

11. A dye salt according to claim 6 wherein the nitrogen base is amember selected from the group consisting of a primary or secondaryaliphatic amine having from 4 to 18 carbon atoms.

12. A dye salt according to claim 6 wherein the nitrogen base is aheterocyclic nitrogen-containing compound of aromatic character selectedfrom the group consisting of an oxazole, a thiazole, a pyrrole, apyrazole, an i'midazole, a thiodiazole, an oxadiazole, a 1,2,3-triazole,a 1,2,4-triazole, a tetrazole, a pyridine, a piperidi-ne, a pyrrolidine,a piperazine, a morpholine, a pyridazine, a pyrazolidine, a pyrazoline,a pyrimidine, a pyrazine, a henzoxazole, a benzthiazole, an indole, anindazole, a henzimidazole, a quinoline and an isoquinoline.

13. A dye salt according to claim 6 wherein the nitrogen base is a basicdye containing a member selected from the group consisting of ahydrazinium, an ammonium, a cycloimmonium and an aminoxide group.

14. A dye salt according to claim 6 wherein the nitrogen base is a basicdye selected from the group consisting of an acridine, an auramine, arhodamine and a triphenylmethane.

15. A dye salt according to claim 14 wherein the nitrogen base is arhodamine.

16. Dye salts according to claim 1 of the formula 1'13 R (IJOOH 1 RF NCo N i c0011 11 ll l f Y 0' =O c=c-co l p aC-C CH3 NH-R 1 \N III 2 s)2 t\0/ 2 s)2' Rio K V Q i v l wherein: a

R is a member selected from the group consisting of R is a memberselected from the group consisting of a substituted and unsubstitutedalkyl radical having hydrogen and nitro, K p p 5 to 14 carbon atoms, 20R is a member selected from the group consisting of R is a memberselected from the group consisting of hydrogen, substituted andunsubstituted alkyl, chlohydrogen, substituted and unsubstituted alkyl,chlorine and bromine, and t rine, bromine and nitro, R is a memberselected from the group consisting of R is a member selected; from thegroup consisting of hydrogen, substituted and unsubstituted alkyl andhydrogen, substituted and unsubstituted alkyl, alkoxy, 25 aryl.chlorine, bromine and {nitro, N I 17. The dye salt of the formula I vCOOH e 4' v fi Co t 5 l c=o-o-- l cm (0 Hum ONHCH:| H

(CHfla-CHQJ 2 18. The dye salt of the formula F j f 10011 -e N\ vC( N u;u

H3o-o I CH NHCH:(|JH

N-a mit-0H8 2 s)2N \O/ n .s)2

I 19. The dye salt of the formula COOH I N-- NH-CHa- H (CH2)3CH3 (CaHahN0 N(C:HB)2

15 16 20. The dye salt of the formula OaN- -O O -NO:

ea N Co N ll H N N CO0H o l H3CC/ C -CO 02H!) C--N NH-CHz- H eba 1 s)2N0 N( s):

21. The dye salt of the formula ti -7% i f -ooo11 c=o c=o- :0 01115 mooI 42H: NH-CHz- H \N-N ah-CH3 (czfinhN \0/ =mclnm 22. The dye salt of theformula OzN O O NO2 ea N- GmN 13 ll -c00n /(|]=C/ 0 Cali! I 1130-0 CH:NH-CH: H

N-N elm-om (CxHshN- \O/ N(C2H5)2 23. A dye salt according to claim 7wherein each metal linkage formed by a metal complex forming substituentis an --O-- bridge; the 4-position of the benzene nucleus of component(a) bears a member selected from the group consisting of hydrogen,chloro, bromo, nitro and a lower alkyl group; R is the carboxylic acidgroup; the other metallizable azo dye is a 2-amino-4-R -5-R -6-Rl-hydroxybenzene1-R -3-methyl-5-pyrazolone, wherein R is a memberselected from the group consisting of hydrogen, chloro, bromo, nitro, alower alkyl group and a lower alkoxy group, R is a member selected fromthe group consisting of hydrogen and nitro, R is a member selected fromthe group consisting of hydrogen, chloro, bromo and a lower alkyl group,and R is a. member selected from the group consisting of hydrogen, alower alkyl group, a phenyl group, a naphthyl group and atetrahydronaphthyl group; and the metal is cobalt.

References Cited UNITED STATES PATENTS 194,999 1/ 1958 Austria.

FLOYD D. HIGEL, Primary Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,406,164 October 15, 1968 Ruedi Altermatt et a1.

It is certified that error appears in the above identified patent andthat said Letters Patent are hereby corrected as shown below:

Columns 9 and 10, in the table, sixth column, opposite Example 51,"NHCOCO should read NHCOCH Columns 11 ant 12, in the table, fifthcolumn, opposite Example 96, "CH CH OCO( should read CH CH OCOCH Columns17 and 18, in the table sixth column, opposite Example 269, "COH CHshould read OCH CH Column 22, line 50, "haloalkoxycarbonylalkyl," shotread haloalkoxycarbonyloxyalkyl, Column 23, line 4"methoxylacetylamino," should read methoxyacetylamino,

Column 24, lines 70 to .75, the lower right-hand of the formula reading"CH CH OCOC" should read CH CH OCOCH Signed and sealed this 10th day ofMarch 1970.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. WILLIAM E. SCHUYLER, JR. Attesting OfficerCommissioner of Patents

